Polyaniline (PANI) is a potential candidate for n-type thermoelectric (TE) materials owing to its intrinsic electrical conductivity, low thermal conductivity, and facile synthesis techniques. However, its low Seebeck coefficient and power factor have limited its widespread usage. In this study, nitrogen-doped, and sulfur-nitrogen co-doped reduced graphene oxide (rGO) were used for tuning the TE properties of PANI. Doped rGO and PANI/doped-rGO nanocomposites were prepared via hydrothermal technique and chemical oxidative polymerization respectively and thereafter characterized. The TE properties of the nanocomposites were also studied and an optimized Seebeck coefficient, power factor and zT value of −1.75 mV K−1, 95 μW m−1 K−2 and 0.06, respectively were reported for the PANI nanocomposite containing 1 wt% sulfur-nitrogen co-doped rGO. These results suggest that PANI/heteroatom-doped rGO can serve as promising candidates for n-type based TE applications.